JP2016523794A - Spherical particles, their production and methods of using them - Google Patents

Abstract

(A) at least one transition metal mixed hydroxide or transition metal mixed carbonate of at least three different transition metals selected from nickel, cobalt, manganese, iron, chromium and vanadium; and (B) Ba, Al, Spherical particles containing at least one fluoride, oxide or hydroxide of Zr or Ti, wherein the transition metal in the transition metal hydroxide (A) or transition metal carbonate (A) is mainly composed of In the +2 oxidation state, fluoride (B) or oxide (B) or hydroxide (B) is present in the form of domains in the outer shell of spherical particles to the extent of at least 75%, transition metal hydroxylation Spherical particles encapsulated to the extent of at least 90% with the product (A) or transition metal carbonate (A).

Description

The present invention
(A) at least one transition metal mixed hydroxide or transition metal mixed carbonate of at least three different transition metals selected from nickel, cobalt, manganese, iron, chromium and vanadium;
(B) Spherical particles containing at least one fluoride, oxide or hydroxide of Ba, Al, Zr or Ti, in transition metal hydroxide (A) or transition metal carbonate (A) These transition metals are mainly in the +2 oxidation state,
Fluoride (B) or oxide (B) or hydroxide (B) is present to the extent of at least 75% in the outer shell of spherical particles in the form of domains, transition metal hydroxide (A) or transition It relates to spherical particles which are encapsulated (covered) to the extent of at least 90% with metal carbonate (A).

  Energy conservation has long been a subject of increasing interest. Electrochemical cells such as batteries or accumulators can serve to store electrical energy. Recently, lithium ion batteries have been of particular interest. They are superior to conventional batteries in several technical aspects. For example, they can be used to generate voltages that cannot be obtained with batteries based on aqueous electrolytes.

  In lithium ion batteries, the material from which the electrode is made, more specifically the material from which the cathode is made, plays an important role.

  In many cases, the active material used is a lithium-containing transition metal mixed oxide, in particular a lithium-containing nickel-cobalt-manganese oxide.

  Many batteries have problems as a result of inadequate cycle stability, lifetime and reliability, especially with regard to short circuits, when there is mechanical damage to the battery or excessive thermal stress, Each of these still needs improvement.

  To solve such problems, lithium-containing nickel-cobalt-manganese oxides doped with one or more metals such as Ba, Zr, Al or Ti have been used, see for example EP2386636 I want to be. Such doped lithium-containing transition metal mixed oxides are typically made in a multi-step process, where a sparingly soluble compound or mixture of sparingly soluble compounds, each also referred to as a precursor, is first transition metal salt. From one or more solutions. This precursor is heat-treated in the second stage, usually in the range of 600 ° C to 1000 ° C. The properties of the precursor have a great influence on the properties of the active material. The precursor can then be coated with a small amount of a Ba, Ti, Al or Zr compound to obtain a precursor coated on the outer surface. In another variation, the procedure is to mix the transition metal salt solution with a soluble compound of Ba, Ti, Al or Zr to precipitate the added metal with the transition metal.

However, the drawback is that coating with compounds that are often non-electrically conductive, such as Al ₂ O ₃ , TiO ₂ or BaO, clearly reduces the power load capability of the battery. Also, in some cases, it is observed that the coated cathode material allows a lower connection of particles to the output conductor. A further disadvantage is that the coating can peel from the rest of the battery material as a result of the aging phenomenon.

  WO 2009/074311 discloses a method for producing a precursor for battery materials, in which a dispersion of titanium dioxide is continuously added during precipitation of a nickel-cobalt-manganese mixed hydroxide. A drawback of the disclosed method is that in many cases titanium dioxide particles are found in battery materials that can have an adverse effect on battery current durability.

EP2238636 WO2009 / 074311

  Thus, the problem addressed is to have improved reliability, especially with respect to short circuits, in the case of mechanical damage to the battery or excessive thermal stress, while on the power load capability. It was a problem to provide a cathode material for lithium ion batteries that did not have to accept the drawbacks. A further problem addressed was first the problem of providing a method for producing a cathode material for lithium ion batteries with improved reliability without having to accept the drawbacks in terms of power load capability.

  Cathode material precursors have been found to have a significant impact on the cathode material. Accordingly, the first defined precursors have been found, which are obtained in the form of spherical particles, and in the context of the present invention, omit the spherical particles of the present invention or otherwise. Called particles of the present invention.

The spherical particles of the present invention are
(A) at least one of at least three different transition metals each selected from nickel, cobalt, manganese, iron, chromium and vanadium, abbreviated in the context of the present invention and also referred to as transition metal hydroxide (A) A transition metal mixed hydroxide, or at least one transition metal mixed carbonate, also referred to as transition metal carbonate (A) for brevity in connection with the present invention;
(B) at least one fluoride, oxide or hydroxide of Ba, Al, Zr or Ti, and the transition metal in the transition metal hydroxide (A) or transition metal carbonate (A) is , Mainly in the +2 oxidation state,
Fluoride (B) or oxide (B) or hydroxide (B) is present to the extent of at least 75% in the outer shell of spherical particles in the form of domains, transition metal hydroxide (A) or transition The metal carbonate (A) is sealed to the extent of at least 90%.

  The particles of the present invention have a spherical shape. Spherical particles are not only those that are strictly spherical, but also include particles in which the maximum and minimum diameters of at least 95% (number average) of a representative sample differ by no more than 5%.

  The transition metal hydroxide (A) is a hydroxide of at least three different transition metals selected from nickel, cobalt, manganese, iron, chromium and vanadium, preferably a mixed hydroxide of nickel, manganese and cobalt . “At least three different transition metal hydroxides” are present not only in their proportions present as trace substances in the particles of the invention, but also in a proportion of at least 1% by weight relative to the total transition metal content of the particles, It shall be understood to mean those proportions preferably present in a proportion of at least 2% by weight, more preferably in a proportion of at least 5% by weight.

  The transition metal hydroxide (A) may contain trace amounts of other metal ions, eg, trace amounts of ubiquitous metals such as sodium, but these are not considered in the description.

  The transition metal hydroxide (A) includes not only hydroxide ions but also counter ions other than hydroxide ions, such as carbonate ions, sulfate ions, nitrate ions, carboxylate ions, particularly acetate ions, or halide ions, In particular, chloride ions may be included. Particularly preferred counter ions other than hydroxide ions are oxide ions combined with sulfate ions in particular. The carbonate ion, sulfate ion, carboxylate ion or halide ion can be present in a trace amount in the transition metal mixed hydroxide (A), for example, up to 1% by mass with respect to the hydroxide. Oxide ions may be present in higher proportions in the transition metal mixed hydroxide (A), for example, every second anion is a hydroxide ion and every second anion is an oxide ion. Also good.

  The transition metal carbonate (A) is a carbonate of at least three different transition metals selected from nickel, cobalt, manganese, iron, chromium and vanadium, preferably a mixed carbonate of nickel, manganese and cobalt. “Carbonates of at least three different transition metals” are preferred not only in their proportions present as trace substances in the particles of the invention, but also in a proportion of at least 1% by weight relative to the total transition metal content of the particles. Is to be understood to mean those proportions present in a proportion of at least 2% by weight, more preferably in a proportion of at least 5% by weight.

  The transition metal carbonate (A) may contain trace amounts of other metal ions, for example, trace amounts of ubiquitous metals such as sodium, but these are not considered in the description.

  The transition metal carbonate (A) is not only a carbonate ion but also a counter ion other than a carbonate ion, such as a hydroxide ion, a sulfate ion, a nitrate ion, a carboxylate ion, particularly an acetate ion, or a halide ion, particularly a chloride. Ions may be included. Particularly preferred counter ions other than carbonate ions are oxide and hydroxide ions, especially in combination with sulfate ions. Hydroxide ions, sulfate ions, carboxylate ions or halide ions can be present in trace amounts in the transition metal mixed carbonate (A), for example, up to 1% by mass with respect to the carbonate. An oxide may be present in a higher proportion in the transition metal mixed carbonate (A). For example, every 3 or less, for example every 10 or less anions may be oxide ions.

  The transition metal hydroxide (A) or transition metal carbonate (A) may contain up to 20 mol% manganese hydroxide or manganese carbonate relative to the cation. In another embodiment of the invention, the transition metal hydroxide (A) or transition metal carbonate (A) does not contain magnesium.

  The particles of the present invention may have a median diameter (D50) measured by light scattering, for example, in the range of 0.1 μm to 35 μm, preferably 2 μm to 30 μm. Good. Suitable instruments are commercially available, for example, a Malvern Mastersizer.

  The width of the particle size distribution is preferably narrow. In one embodiment of the invention, (D10) ≧ 3 μm and (D90) <30 μm for the particles of the invention. Further, in certain embodiments of the invention, 3 (D10) ≧ (D50) and (D90) ≦ 2 (D50). More preferably, 2 (D10) ≧ (D50) and (D90) ≦ 1.5 (D50).

  The transition metal in the transition metal hydroxide (A) or transition metal carbonate (A) is mainly in the +2 oxidation state. This is because at least 50 mol% of the transition metal in the transition metal hydroxide (A) or transition metal carbonate (A) selected from nickel, cobalt, manganese, iron, chromium and vanadium is in the +2 oxidation state 50 mol% or less, preferably 40 mol% or less, is understood to mean that it may be in the +3 or +4 oxidation state. The oxidation state can be determined, for example, by redox titration. In certain embodiments of the invention, all transition metals in the transition metal hydroxide (A) or transition metal carbonate (A) are in the +2 oxidation state and the transition metals are from nickel, cobalt and manganese. Selected.

Figure 1 shows the aluminum selective analysis of the precursor according to Example I.1.

  In one embodiment of the invention, all transition metals in the transition metal hydroxide (A) or transition metal carbonate (A) are in the +2 oxidation state.

  In one embodiment of the present invention, 1 to 40 mol% of manganese in transition metal hydroxide (A) or transition metal carbonate (A) is in the +4 oxidation state and the remainder of manganese is in the +2 oxidation state.

  In one embodiment of the present invention, 1-40 mol% of cobalt in the transition metal hydroxide (A) or transition metal carbonate (A) is in the +3 oxidation state and the remainder of the cobalt is in the +2 oxidation state. Preferably, nickel is only in the +2 oxidation state.

The particles of the present invention comprise (B) at least one fluoride of Ba, Al, Zr or Ti, also referred to as fluoride (B), oxide (B) or hydroxide (B) in connection with the present invention. Further comprising an oxide or hydroxide. Examples of fluoride (B) are AlF ₃ , BaF ₂ , ZrF ₄ and TiF ₄ . Examples of oxides (B) are BaO, Al ₂ O ₃ , ZrO ₂ and TiO ₂ , and furthermore BaTiO ₃ and BaZrO ₃ . Examples of hydroxides are those having a defined formula, such as Ba (OH) _{2 as} well as water-containing oxides such as Al ₂ O ₃ aq, TiO ₂ aq and ZrO ₂ aq, and basic hydroxylation Product, such as AlOOH. Preferred oxides (B) or hydroxides (B) are selected from BaTiO ₃ , Al ₂ O ₃ and TiO ₂ .

  In the particles of the invention, fluoride (B) and / or oxide (B) and / or hydroxide (B) are in the form of domains, preferably to the extent of at least 75% in the outer shell of the spherical particles, preferably To the extent of at least 90%, more preferably completely present, encapsulated by transition metal hydroxide (A) or transition metal carbonate (A) to at least 90%.

  Domain means a region of a particle of the invention in which the content of fluoride (B), oxide (B) or hydroxide (B) is at least 20 mol% higher than the rest of the particle Understood. In certain embodiments of the invention, only fluoride (B), oxide (B) or hydroxide (B) is present in the domain.

  Less than 25%, preferably up to 10%, more preferably unmeasurable proportions of fluoride (B) or oxide (B) or hydroxide (B) are localized in the core of the particles of the invention. ing.

  The domain may have a diameter in the range of 10 nm up to 1 μm and may have a spherical, oval or irregular shape. The domain may have a crystalline or amorphous structure.

  In relation to the domain, “encapsulated to the extent of at least 90% by transition metal hydroxide (A) or transition metal carbonate (A)” refers to the fluoride (B) or oxide (B) Alternatively, at least 90% of the hydroxide (B) is encapsulated with the transition metal hydroxide (A) or the transition metal carbonate (A), and the fluoride (B) or oxide (B) or hydroxide. It is understood that 10% or less of (B) is on the outermost surface of the particles of the present invention.

  The core and outer shell of the particles of the present invention may have different diameters. The diameter of the core should preferably comprise at least 50% of the particles of the invention. In a preferred embodiment of the invention, the outer shell has an average thickness of 1% to 15% for each particle diameter.

  The domain, its composition and its thickness can be determined, for example, by electron microscopy, such as scanning electron microscopy.

  In one embodiment of the present invention, the proportion of fluoride (B) or oxide (B) or hydroxide (B) is 0 relative to transition metal hydroxide (A) or transition metal carbonate (A). Within the range of 3% to 5% by weight.

In one embodiment of the present invention, the transition metal mixed hydroxide (A) has the general formula (I)
Ni _a Co _b Mn _c M _d O _e (OH) _f (I)
(Where the signs (variables) are defined as follows:
M is one or more transition metals selected from Mg and / or Fe, Cr and V;
a is in the range of 0.1 to 0.8, preferably 0.5 to 0.65;
b is in the range of 0.07 to 0.4, preferably 0.15 to 0.25;
c is in the range of 0.07 to 0.6, preferably 0.15 to 0.25;
d is in the range of zero to 0.2, preferably 0.05;
a + b + c + d = 1,
e is in the range of 0.05 to 0.5, preferably 0.4,
f is in the range of 0.5 to 1.9, preferably at least 1.2;
The average oxidation state of Ni, Co and Mn is in the range of 2.1 to 3.2).

  The average oxidation state of Ni, Co and Mn is understood to mean the oxidation state averaged over all transition metals in the particle of the invention.

  For example, when e = 0.5 and f = 1.5, the average oxidation state of Ni, Co and Mn is 2.5, and when e = 0.5 and f = 1.9, Ni, Co and The average oxidation state of Mn is 2.9.

In one embodiment of the present invention, the transition metal mixed carbonate (A) has the general formula (II)
Ni _{a ′} Co _{b ′} Mn _{c ′} M _{d ′} O _{e ′} (OH) _j (CO ₃ ) _h (II)
(In the formula, each variable is defined as follows:
M is Mg and / or one or more transition metals selected from Fe, Cr and V;
a ′ is in the range of 0.1 to 0.5, preferably 0.2 to 0.3;
b ′ is in the range of zero to 0.3, preferably zero to 0.15;
c ′ is in the range of 0.1 to 0.75, preferably 0.45 to 0.75;
d ′ is in the range of zero to 0.2, preferably zero to 0.05;
a ′ + b ′ + c ′ + d ′ = 1,
e ′ is in the range of zero to 0.6;
h is in the range of 0.4 to 1;
j is in the range of zero to 0.3).

  In one embodiment of the present invention, the particles of the present invention are of a uniform composition with respect to the transition metals nickel, cobalt, manganese, chromium, vanadium and iron, which varies in relative composition across the particle's cross section. Means no. In another embodiment of the invention, the inventive particles of the sample are of heterogeneous composition, in which case the composition of nickel, cobalt, manganese, chromium, vanadium and iron, preferably of nickel, cobalt and manganese. The average standard deviation of the composition is in each case up to 10 mol%. In certain embodiments, the particles of the present invention are of a non-homogeneous composition, wherein the particles consist of primary particles which, on the other hand, have a non-homogeneous composition, wherein the composition of nickel, cobalt, manganese, chromium, vanadium and iron Preferably, the mean standard deviation of the composition of nickel, cobalt and manganese is in each case up to 10 mol%, but the various particles of the sample may be of essentially the same composition.

  The present invention further provides a method for producing the particles of the present invention, also referred to in the context of the present invention as the production method of the present invention.

In one embodiment of the invention, the procedure is as follows:
(A) First, particles of transition metal hydroxide (A) or transition metal carbonate (A) are produced,
(B) Fluoride (B) or oxide (B) or hydroxide (B), or a solution comprising a salt of Ba, Al, Zr or Ti and optionally a water-soluble fluoride, particles according to step (a) And at a different time or place from step (a),
(C) Further transition metal hydroxide (A) or transition metal carbonate (A) is produced during step (c) and thus obtained transition metal hydroxide (A) or transition metal carbonate Salt (A) is combined with the particles from step (b),
Steps (b) and (c) may be performed simultaneously or sequentially.

  In step (b), it can proceed from fluoride (B) or oxide (B) or hydroxide (B), or fluoride (B) or oxide (B) or hydroxide (B) is generated in situ.

  By contact in step (b), fluoride (B) or oxide (B) or hydroxide (B) is applied to the particles from step (a).

  In embodiments where a solution comprising a water-soluble salt of Ba, Al, Zr or Ti or optionally a water-soluble fluoride is used, the type of solution is a hydroxide, oxide and fluoride of Ba, Al, Zr and Ti. A water-insoluble compound selected from the compounds is selected to at least partially precipitate under the reaction conditions of step (b). These water-insoluble compounds are separated on the particles from step (a) under the reaction conditions of step (b).

  The particles of the present invention can be produced in a batch or continuous procedure. It is preferred to produce the particles of the present invention by precipitation from an aqueous solution.

  Semi-continuous processes are also conceivable.

  If it is desired to produce the particles of the present invention batchwise, the procedure is for example first in the form of particles having an average diameter smaller than the particles of the present invention, first the transition metal hydroxide (A) or The transition metal carbonate (A) may be generated in a stirring vessel (step (a)). The particles thus formed are generally obtained as a suspension. The oxide (B), fluoride (B) or hydroxide (B) particles are then added to the suspension thus formed, or soluble compounds of titanium, zirconium, barium or aluminum are added. And optionally further precipitation reagents such as water-soluble fluoride are added (step (b)). Simultaneously or subsequently, further transition metal hydroxides (A) or transition metal carbonates (A) or transition metal carbonates (A), for example by further precipitation or reprecipitation A) is generated (step (c)).

  Specifically, for example, it is possible to proceed as follows. In a stirred vessel at least three different transition metal salts selected from, for example, halides, nitrates, carboxylates, in particular acetates, or most preferably nickel, cobalt, manganese, iron, chromium and vanadium as sulfates Is combined with at least one precipitation reagent, such as at least one alkali metal hydroxide or alkali metal carbonate or ammonium carbonate, to form a transition metal hydroxide (A) or transition metal carbonate (A). It is precipitated (step (a)). Thereafter, fluoride (B), hydroxide (B) or oxide (B) is added in the form of particles or in the form of a suspension (step (b)), and further the transition metal, nickel An aqueous solution of cobalt, manganese, iron, chromium and / or vanadium, nitrate, carboxylate, especially acetate, or most preferably sulfate, and additional precipitation reagents are added (step (c)).

  In another specific embodiment, it can proceed as follows. In a stirred vessel at least three different transition metal salts selected from, for example, halides, nitrates, carboxylates, in particular acetates, or most preferably nickel, cobalt, manganese, iron, chromium and vanadium as sulfates Is combined with at least one precipitation reagent, such as at least one alkali metal hydroxide or alkali metal carbonate or ammonium carbonate, to form a transition metal hydroxide (A) or transition metal carbonate (A). It is precipitated (step (a)). Thereafter, a soluble compound of titanium, zirconium, barium or aluminum is added, optionally with a water-soluble fluoride, such as sodium fluoride or ammonium fluoride (step (b)). Simultaneously or subsequently, an additional aqueous solution of a salt of a transition metal selected from nickel, cobalt, manganese, iron, chromium and vanadium and an additional precipitation reagent are added (step (c)).

  In embodiments where a soluble barium compound is used to precipitate fluoride (B), hydroxide (B) or oxide (B), the soluble salt of the transition metal is not selected from sulfate.

In embodiments where it is desirable to produce transition metal hydroxides (A) or transition metal carbonates (A) that also contain M, defined as Mg, at least one magnesium compound, preferably a water soluble magnesium compound, such as MgSO ₄ is also added. The addition of the magnesium compound can be achieved, for example, during step (a) or step (c) or in a separate step.

  In another embodiment, the particles of the present invention are produced by a continuous process. For this, the procedure may specifically be to use a stirred tank cascade with at least two stirred tanks. In the first stirred tank, the transition metal hydroxide (A) or the transition metal carbonate (A) is produced in the form of particles having an average diameter smaller than that of the particles of the present invention (step ( a)). The particles thus formed are generally obtained as a suspension. This suspension is in the form of particles or suspension in the form of fluoride (B), hydroxide (B) or oxide (B) (step (b)), the transition metal, nickel, First charge of cobalt, manganese, iron, chromium and / or vanadium halide, nitrate, carboxylate, especially acetate, or most preferably sulfate aqueous solution, and further precipitation reagent (step (c)) Transfer to a second stirred tank containing or metered in.

  In another specific embodiment, it can proceed as follows. A stirred tank cascade with at least two stirred tanks is used. In the first stirred tank, the transition metal hydroxide (A) or the transition metal carbonate (A) is produced in the form of particles having an average diameter smaller than that of the particles of the present invention (step ( a)). The particles thus formed are generally obtained as a suspension. This suspension contains the initial charge of fluoride (B), hydroxide (B) or oxide (B) in the form of particles or suspension, or it is metered in The second stirring tank is transferred (step (b)). The suspension thus obtained is a further transition metal, nickel, cobalt, manganese, iron, chromium and / or vanadium halide, nitrate, carboxylate, in particular acetate, or most preferably further sulfate. The aqueous solution is transferred to a third stirred tank with additional precipitation reagent added (step (c)).

  In another specific embodiment, it can proceed as follows. A stirred tank cascade with at least two stirred tanks is used. In the first stirred tank, the transition metal hydroxide (A) or the transition metal carbonate (A) is produced in the form of particles having an average diameter smaller than that of the particles of the present invention (step ( a)). The particles thus formed are generally obtained as a suspension. This suspension comprises a soluble compound of titanium, zirconium, barium or aluminum, and optionally a water-soluble fluoride such as sodium fluoride or ammonium fluoride (step (b)), as well as the transition metal, nickel, Second, to which an aqueous solution of cobalt, manganese, iron, chromium and / or vanadium, nitrate, carboxylate, in particular acetate, or most preferably sulfate, and further precipitation reagent (step (c)) is added. To the stirred tank.

  In another specific embodiment, it can proceed as follows. A stirred tank cascade with at least two stirred tanks is used. In the first stirred tank, the transition metal hydroxide (A) or the transition metal carbonate (A) is produced in the form of particles having an average diameter smaller than that of the particles of the present invention (step ( a)). The particles thus formed are generally obtained as a suspension. This suspension is transferred to a second stirred tank to which a soluble compound of titanium, zirconium, barium or aluminum, and optionally a water-soluble fluoride such as sodium fluoride or ammonium fluoride is added (step (b) )). The suspension thus obtained is a further transition metal, nickel, cobalt, manganese, iron, chromium and / or vanadium halide, nitrate, carboxylate, in particular acetate, or most preferably further sulfate. The aqueous solution is transferred to a third stirred tank with additional precipitation reagent added (step (c)).

In embodiments where it is desirable to produce transition metal hydroxides (A) or transition metal carbonates (A) that also contain M, defined as Mg, at least one magnesium compound, preferably a water soluble magnesium compound, such as MgSO ₄ is also added. The magnesium compound can be added at any point in the cascade.

  In one embodiment of the invention, the method of the invention is performed at a temperature in the range of 10 ° C to 85 ° C, preferably in the range of 20 ° C to 50 ° C.

  In one embodiment of the present invention, the method of the present invention is an 8 to 12, preferably 10.5 to 12.0, more preferably 11.3 to 11.9, each measured at 23 ° C. in the mother liquor. Performed at a pH within the range.

  In one embodiment of the invention, the method of the invention is performed at a pressure in the range of 500 mbar to 20 bar, preferably at standard pressure.

  In one embodiment of the invention, an excess of a precipitating agent, such as an alkali metal hydroxide or alkali metal carbonate, is used with respect to the transition metal. The molar excess may be, for example, in the range of 1.1: 1 to 100: 1. Treatment with a stoichiometric proportion of precipitant is preferred.

In one embodiment of the present invention, the aqueous alkali metal hydroxide solution has an alkali metal hydroxide concentration in the range of 1% to 50% by weight, preferably 10% to 25% by weight. In another embodiment of the invention, the aqueous solution of the alkali metal carbonate (hydrogen) salt is from 1% by weight to the maximum of the saturated solution, in the case of NaHCO ₃ up to 10% by weight, in the case of Na ₂ CO ₃ 21. It has an alkali metal carbonate (hydrogen) salt in a concentration of up to 5% by weight (in each case the value at 20 ° C. or higher at correspondingly higher temperatures).

  In one embodiment of the present invention, the concentration of the aqueous solution of the transition metal salt can be selected within a wide range. Preferably, the concentrations are selected such that they are in the range of 1 to 1.8 moles transition metal / kg solution, more preferably 1.5 to 1.7 moles transition metal / kg solution. Is done.

  In one embodiment of the invention, the process according to the invention is carried out in the presence of at least one compound L which can function as a ligand for at least one of the transition metals, for example at least one organic amine or in particular ammonia. Done in the presence of In the context of the present invention, water should not be regarded as a ligand.

In one embodiment of the invention, a concentration of L, in particular ammonia, in the range of 0.05 mol / l to 1 mol / l, preferably 0.1 mol / l to 0.7 mol / l is selected. . Particularly preferred is an amount of ammonia in which the solubility of Ni ²⁺ in the mother liquor is 1000 ppm or less, more preferably 500 ppm or less.

  In one embodiment of the invention, mixing is achieved during the production of the particles of the invention, for example by means of a stirrer. It is preferred to introduce an agitator output of at least 1 W / l, preferably at least 3 W / l, more preferably at least 5 W / l into the reaction mixture. In one embodiment of the invention, an agitator output of 25 W / l or less can be introduced into the reaction mixture.

  In certain embodiments of the invention, the procedure may be to reduce the stirrer output towards the end of the batch operation in the case of a batch process variation.

  In one embodiment of the invention, the mother liquor is removed during the performance of the method of the invention.

  The method of the present invention may be carried out in the presence or absence of a reducing agent. Examples of suitable reducing agents are hydrazine, ascorbic acid, glucose and alkali metal sulfites. It is preferred not to use any reducing agent.

The method of the invention may be carried out under air, under an inert gas atmosphere, for example under a noble gas or nitrogen atmosphere, or under a reducing atmosphere. Examples of the reducing gas is, for example, SO _2. Treatment in an inert gas atmosphere is preferred.

  After actual production, the particles of the invention are removed from the mother liquor. Removal can be achieved, for example, by filtration, centrifugation, decantation, spray drying or sedimentation, or by a combination of two or more of the above operations. Suitable devices are, for example, filter presses, belt filters, spray dryers, hydrocyclones, gradient purifiers, or combinations of the devices described above.

  Mother liquor refers to water, water soluble salts, and any additional additives present in the solution. Water-soluble salts are, for example, alkali metal salts of transition metal counterions, such as sodium acetate, potassium acetate, sodium sulfate, potassium sulfate, sodium nitrate, potassium nitrate, sodium halide, in particular sodium chloride, potassium halide, and more Salt, optional additives used, and any excess alkali metal carbonate or hydroxide, and also ligand L. Furthermore, the mother liquor may contain a trace amount of a soluble transition metal salt.

  In one embodiment of the invention, the mother liquor can be removed using an impact purifier divided into two sections, not only the precipitated particles are removed, but also a suspension by stirring in a stirring vessel. The introduced bubbles are also removed.

  After actual removal, the particles of the present invention can be washed. Washing can be achieved, for example, with pure water or with an aqueous solution of an alkali metal carbonate or alkali metal hydroxide, in particular with an aqueous solution of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide or ammonia. Water and aqueous solutions of alkali metal hydroxides, particularly sodium hydroxide are preferred.

  Washing may be accomplished, for example, with the use of elevated pressure or elevated temperature such as 30 ° C to 50 ° C. In another variation, the cleaning is performed at room temperature. The efficiency of the wash can be confirmed by an analytical scale. For example, the content of transition metals in the wash water can be analyzed.

  If washing is accomplished with water rather than an aqueous solution of an alkali metal hydroxide, a conductivity test on the wash water can be used to determine whether water soluble substances, such as water soluble salts, can still be washed away. It is.

Drying may be performed after removal of the particles of the present invention. Drying may be performed, for example, with an inert gas or air. Drying may be performed at a temperature in the range of 30 ° C. to 150 ° C., for example. When drying is performed in air, in many cases it is observed that some transition metals are partially oxidized, eg Mn ²⁺ is oxidized to Mn ⁴⁺ and Co ²⁺ is oxidized to Co ^3+. The blackening is observed.

  The particles of the present invention have good suitability for conversion to cathode materials for lithium ion batteries. Accordingly, the present invention further provides a method of using the particles of the present invention to produce lithium-containing transition metal mixed oxides. The present invention further provides a method for producing lithium-containing transition metal mixed oxides using the particles of the present invention, also abbreviated as the method of the present invention.

  In order to carry out the method of the invention, the procedure is, for example, mixing the particles of the invention with at least one lithium compound and reacting them at a temperature in the range of 500 ° C. to 1000 ° C. Also good.

The selected lithium compound is preferably a lithium salt, each in the anhydrous form or as a hydrate, if present, such as Li ₂ O, LiOH, LiNO ₃ , Li ₂ SO ₄ , LiCl or Li ₂ CO ₃ , LiOH is preferable, and Li ₂ CO ₃ is particularly preferable.

  The amount of particles and lithium compound of the present invention is selected so as to obtain the desired stoichiometry of the cathode material. The molar ratio of lithium to the total of all transition metals and any M is in the range of 1: 1 to 1.4: 1, preferably 1.01: 1 to 1.1: 1. It is preferred to select the particles and the lithium compound.

  The reaction at 500 ° C. to 1000 ° C. may be performed in a furnace, for example, in a rotary tube furnace, a muffle furnace, a pendulum furnace, a roller hearth furnace, or a push-through furnace. Combinations of two or more of the above mentioned furnaces are also possible.

  The reaction at 500 ° C. to 1000 ° C. may be performed over a period of 30 minutes to 24 hours. The reaction may be accomplished at one temperature or a temperature profile may be performed.

  Implementation of the method of the present invention results in a lithium-containing transition metal mixed oxide that also forms part of the inventive subject matter.

In particular, the present invention provides a lithium-containing transition metal mixed oxide in the form of fine particles, which is omitted and referred to as the mixed oxide of the present invention. The mixed oxide of the present invention is
(C) at least one mixed oxide of lithium and at least three different transition metals selected from nickel, cobalt, manganese, iron, chromium and vanadium, also referred to as oxide (C) for short
(D) at least one fluoride or oxide of Ba, Al, Zr or Ti, wherein the fluoride (D) or oxide (D) is at least 75% in the outer shell of the particles in the form of domains And is enclosed to the extent of at least 90% by the oxide (C).

  The mixed oxide of the present invention is in the form of spherical particles. Spherical particles, as in the case of the particles of the present invention, include not only strictly spherical particles, but also particles whose maximum and minimum diameters of at least 95% (number average) of a representative sample differ by no more than 5%. Shall be.

  It is observed that the mobility of transition metal ions selected from nickel, cobalt, manganese, iron, chromium and vanadium ions within the particles is very low during the process of the invention, depending on the temperature. On the other hand, Ba, Al, Zr or Ti ions may migrate or diffuse during the performance of the method of the invention. Thus, the statements made regarding the uniformity of shells, domains and compositions associated with the particles of the present invention can be applied accordingly to the mixed oxides of the present invention. On the other hand, when the treatment is achieved at 950 ° C. to 1000 ° C. for more than 12 hours, it is generally found that Ba, Al, Zr or Ti ions are uniformly distributed across the cross section of the mixed oxide particles.

  In one embodiment of the present invention, the mixed oxide particles of the present invention are present in the form of aggregates of primary particles. The primary particles may have an average diameter in the range of 10 nm to 500 nm, for example. The mixed oxide particles of the present invention may have a median diameter (D50) in the range of 0.1 μm to 35 μm, preferably 2 μm to 30 μm, as measured, for example, by light scattering. Suitable instruments are commercially available, for example, a Malvern Mastersizer.

  The width of the particle size distribution is preferably narrow. In one embodiment of the invention, (D10) ≧ 3 μm and (D90) <30 μm for the mixed oxide particles of the invention. Further, in certain embodiments of the invention, 3 (D10) ≧ (D50) and (D90) ≦ 2 (D50). More preferably, 2 (D10) ≧ (D50) and (D90) ≦ 1.5 (D50).

  The present invention further provides methods of using the mixed oxides of the present invention as, or for the production of, cathode materials for lithium ion batteries.

  The cathode material may contain carbon as an electrically conductive polymorph, such as carbon black, graphite, graphene, carbon nanotubes or activated carbon, as well as the mixed oxides of the present invention.

  The cathode material may further comprise at least one binder, such as a polymer binder.

  Suitable binders are preferably selected from organic (co) polymers. Suitable (co) polymers, i.e. homopolymers or copolymers, are, for example, from (co) polymers obtained by anion, catalysis or free radical (co) polymerization, in particular polyethylene, polyacrylonitrile, polybutadiene, polystyrene and also ethylene, propylene , Styrene, (meth) acrylonitrile and 1,3-butadiene may be selected from copolymers of at least two comonomers. Polypropylene is also suitable. In addition, polyisoprene and polyacrylates are additionally suitable. Polyacrylonitrile is particularly preferred.

  Polyacrylonitrile is understood in the context of the present invention to mean not only polyacrylonitrile homopolymers but also copolymers of acrylonitrile with 1,3-butadiene or styrene. Polyacrylonitrile homopolymer is particularly preferred.

In the context of the present invention, polyethylene is not only homopolyethylene, but also at least 50 mol% of copolymerized form of ethylene and at most 50 mol% of at least one further comonomer, for example propylene, butylene (1-butene), Α-olefins such as 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-pentene and further isobutene, vinyl aromatics such as styrene, and also (meth) acrylic acid, vinyl acetate, vinyl propionate, (meth) acrylic acid _C 1 _{-C 10} of - alkyl esters, especially methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n- butyl acrylate, 2-ethylhexyl acrylate, n- butyl methacrylate, 2-ethylhexyl methacrylate And also maleic acid, maleic anhydride, and itaconic anhydride, are understood to mean also copolymers of ethylene. The polyethylene may be HDPE or LDPE.

  In the context of the present invention, polypropylene is not only homopolypropylene, but also at least 50 mol% of propylene in copolymerized form, and up to 50 mol% of at least one further comonomer, such as ethylene, butylene, 1-hexene, It is also understood to mean copolymers of propylene containing α-olefins such as 1-octene, 1-decene, 1-dodecene and 1-pentene. The polypropylene is preferably isotactic or essentially isotactic polypropylene.

In the context of the present invention, polystyrene is not only a homopolymer of styrene, but also acrylonitrile, 1,3-butadiene, (meth) acrylic acid, C ₁ -C ₁₀ -alkyl esters of (meth) acrylic acid, divinylbenzene, In particular, it is understood to mean copolymers with 1,3-divinylbenzene, 1,2-diphenylethylene and α-methylstyrene.

  Another preferred binder is polybutadiene.

  Other suitable binders are selected from polyethylene oxide (PEO), cellulose, carboxymethylcellulose, polyimide and polyvinyl alcohol.

In one embodiment of the invention, the binder is selected from (co) polymers having an average molecular weight _Mw in the range from 50000 g / mol to 1000000 g / mol, preferably from 500000 g / mol.

  The binder may be a crosslinked or non-crosslinked (co) polymer.

  In a particularly preferred embodiment of the invention, the binder is selected from halogenated (co) polymers, in particular from fluorinated (co) polymers. The halogenated or fluorinated (co) polymer is in copolymerized form at least one having at least one halogen atom or at least one fluorine atom per molecule, preferably at least two halogen atoms or at least two fluorine atoms per molecule. It is understood to mean a (co) polymer comprising

  Examples are polyvinyl chloride, polyvinylidene chloride, polytetrafluoroethylene, polyvinylidene fluoride (PVdF), tetrafluoroethylene-hexafluoropropylene copolymer, vinylidene fluoride-hexafluoropropylene copolymer (PVdF-HFP), vinylidene fluoride. Tetrafluoroethylene copolymers, perfluoroalkyl vinyl ether copolymers, ethylene-tetrafluoroethylene copolymers, vinylidene fluoride-chlorotrifluoroethylene copolymers, and ethylene-chlorofluoroethylene copolymers.

  Suitable binders are in particular polyvinyl alcohols and halogenated (co) polymers such as polyvinyl chloride or polyvinylidene chloride, in particular fluorinated (co) polymers such as polyvinyl fluoride and in particular polyvinylidene fluoride, and polytetrafluoro Ethylene. The electrically conductive carbonaceous material can be selected from, for example, graphite, carbon black, carbon nanotubes, graphene, and a mixture of at least two of the above substances. In the context of the present invention, the electrically conductive carbonaceous material can also be omitted and referred to as carbon (B).

  In one embodiment of the invention, the electrically conductive carbonaceous material is carbon black. The carbon black can be selected from, for example, lamp black, furnace black, frame black, thermal black, acetylene black, and industrial black. Carbon black may contain impurities, such as hydrocarbons, especially aromatic hydrocarbons, or oxygen-containing compounds or oxygen-containing groups, such as OH groups. In addition, sulfur or iron containing impurities in the carbon black are possible.

  In one variation, the electrically conductive carbonaceous material is partially oxidized carbon black.

  In one embodiment of the present invention, the electrically conductive carbonaceous material includes carbon nanotubes. Carbon nanotubes (CNT for short), such as single-walled carbon nanotubes (SWCNT) and preferably multi-walled carbon nanotubes (MWCNT) are known per se. Methods and some properties for generating it are described, for example, in A. Jess et al., Chemie Ingenieur Technik 2006, 78, 94-100.

  In one embodiment of the invention, the carbon nanotubes have a diameter in the range of 0.4 nm to 50 nm, preferably 1 nm to 25 nm.

  In one embodiment of the invention, the carbon nanotubes have a length in the range of 10 nm to 1 mm, preferably 100 nm to 500 nm.

  In the context of the present invention, graphene is understood to mean a nearly ideally or ideally two-dimensional hexagonal carbon crystal with a structure similar to an individual graphite layer.

  In one embodiment of the present invention, the mass ratio of the modified transition metal mixed oxide and electrically conductive carbonaceous material of the present invention is 200: 1 to 5: 1, preferably 100: 1 to 10: 1. .

  A further aspect of the present invention is a cathode comprising at least one transition metal mixed oxide produced as described above, at least one electrically conductive carbonaceous material and at least one binder.

  The mixed oxide and electrically conductive carbonaceous material of the present invention has been described above.

  The present invention further provides an electrochemical cell made using at least one inventive cathode. The present invention further provides an electrochemical cell comprising at least one inventive cathode.

In one embodiment of the invention, the cathode material produced according to the invention is
A mixed oxide of the present invention in the range of 60% to 98% by weight, preferably 70% to 96% by weight;
A binder in the range of 1% to 20% by weight, preferably 2% to 15% by weight;
1% to 25% by weight, preferably 2% to 20% by weight of electrically conductive carbonaceous material.

  The cathode configuration of the present invention can be selected within wide limits. The cathode of the present invention is preferably formed as a thin film, for example, as a film having a thickness in the range of 10 μm to 250 μm, preferably 20 μm to 130 μm.

  In one embodiment of the invention, the cathode of the invention comprises a foil or film that may be untreated or siliconized, such as a metal foil, in particular an aluminum foil, or a polymer film, such as a polyester film.

  The invention further provides a method of using the cathode material of the invention or the cathode of the invention in an electrochemical cell. The present invention further provides a method for producing an electrochemical cell using the cathode material of the present invention or the cathode of the present invention. The present invention further provides an electrochemical cell comprising at least one inventive cathode material or at least one inventive cathode.

  The electrochemical cell of the present invention is defined as an anode in the context of the present invention and comprises a counter electrode which may be, for example, a carbon anode, in particular a graphite anode, a lithium anode, a silicon anode or a lithium titanate anode.

  The electrochemical cell of the present invention may be, for example, a battery or a storage battery.

  The electrochemical cell of the present invention, like the anode and the cathode of the present invention, has additional components such as conductive salts, non-aqueous solvents, partition walls such as output conductors made of metals or alloys, and cable connections and enclosures. You may have a body.

  In one embodiment of the invention, the electrical cell of the invention is preferably at room temperature, selected from polymers, cyclic or acyclic ethers, cyclic and acyclic acetals, and cyclic or acyclic organic carbonates. And at least one non-aqueous solvent, which may be liquid or solid.

Examples of suitable polymers are in particular polyalkylene glycols, preferably poly-C ₁ -C ₄ -alkylene glycols, in particular polyethylene glycol. The polyethylene glycol may comprise _one or more C ₁ -C ₄ -alkylene glycols in copolymerized form up to 20 mol%. The polyalkylene glycol is preferably a double methyl or ethyl capped polyalkylene glycol.

Suitable polyalkylene glycols, in particular suitable polyethylene glycols, may have a molecular weight _Mw of at least 400 g / mol.

The molecular weight _Mw of suitable polyalkylene glycols, in particular suitable polyethylene glycols, may be up to 5000000 g / mol, preferably up to 2000000 g / mol.

  Examples of suitable acyclic ethers are, for example, diisopropyl ether, di-n-butyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, with 1,2-dimethoxyethane being preferred.

  Examples of suitable cyclic ethers are tetrahydrofuran and 1,4-dioxane.

  Examples of suitable acyclic acetals are, for example, dimethoxymethane, diethoxymethane, 1,1-dimethoxyethane and 1,1-diethoxyethane.

  Examples of suitable cyclic acetals are 1,3-dioxane, and in particular 1,3-dioxolane.

  Examples of suitable acyclic organic carbonates are dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate.

（式中、Ｒ^１、Ｒ^２およびＲ^３は、同じまたは異なっていてもよく、それぞれ、水素ならびにＣ_１〜Ｃ_４−アルキル、例えばメチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、イソブチル、ｓｅｃ−ブチルおよびｔｅｒｔ−ブチルから選択され、Ｒ^２およびＲ^３は、好ましくは、両方ともｔｅｒｔ−ブチルではない）の化合物である。 Examples of suitable cyclic organic carbonates are the general formulas (III) and (IV)

Wherein R ¹ , R ² and R ³ may be the same or different and each is hydrogen and C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, respectively. , Sec-butyl and tert-butyl, wherein R ² and R ³ are preferably not both tert-butyl).

In particularly preferred embodiments, R ¹ is methyl, R ² and R ³ are each hydrogen, or R ¹ , R ² and R ³ are each hydrogen.

  Another preferred cyclic organic carbonate is vinylene carbonate of formula (V).

  Preference is given to using solvents in the so-called anhydrous state, ie with a water content in the range from 1 ppm to 0.1% by weight, which can be determined, for example, by Karl Fischer titration.

The electrochemical cell of the present invention further comprises at least one conductive salt. Suitable conductive salts are in particular lithium salts. Examples of suitable lithium salts are LiPF ₆ , LiBF ₄ , LiClO ₄ , LiAsF ₆ , LiCF ₃ SO ₃ , LiC (C _n F _{2n + 1} SO ₂ ) ₃ , lithium imides such as LiN (C _n F _{2n + 1} SO ₂ ) ₂ Where n is an integer in the range of 1 to 20, LiN (SO ₂ F) ₂ , Li ₂ SiF ₆ , LiSbF ₆ , LiAlCl ₄ , and the general formula (C _n F _{2n + 1} SO ₂ ) _t A salt of YLi (wherein t is defined as follows).

When Y is selected from hydrogen and sulfur, t = 1,
T = 2 if Y is selected from nitrogen and phosphorus, and t = 3 if Y is selected from carbon and silicon.

Preferred conductive salts are selected from LiC (CF ₃ SO ₂ ) ₃ , LiN (CF ₃ SO ₂ ) ₂ , LiPF ₆ , LiBF ₄ , LiClO ₄ , with LiPF ₆ and LiN (CF ₃ SO ₂ ) ₂ being particularly preferred. .

  In one embodiment of the present invention, the electrochemical cell of the present invention comprises one or more barriers by which the electrodes are mechanically separated from one another. Suitable partition walls are polymer films that are non-reactive with metallic lithium, especially porous polymer films. Particularly suitable materials for the partition walls are polyolefins, especially porous polyethylene films and porous polypropylene films.

  In particular, polyethylene or polypropylene polyolefin partition walls may have a porosity in the range of 35% to 45%. A suitable pore size is, for example, in the range of 30 nm to 500 nm.

  In another embodiment of the present invention, the septum may be selected from a PET nonwoven filled with inorganic particles. Such partition walls may have a porosity in the range of 40% to 55%. A suitable pore size is, for example, in the range of 80 nm to 750 nm.

  The electrochemical cell of the present invention further comprises a housing that may be of any shape, such as a cube-like or flat cylindrical shape. In one variant, the housing used is a metal foil processed as a bag.

  The electrochemical cell of the present invention provides a high voltage and is excellent with respect to high energy density and good stability. It can be seen that in the electrochemical cell of the present invention, only a low concentration of HF is present in the electrolyte.

  The electrochemical cells of the present invention may be combined with each other, for example, in series connection or parallel connection. A series connection is preferred.

  The present invention further provides a method of using the electrochemical cell of the present invention in a device, particularly a mobile device. Examples of mobile devices are vehicles such as cars, bicycles, airplanes, or water vehicles such as boats or ships. Other examples of mobile devices are portable ones such as computers, especially laptops, telephones, or power tools such as, for example, the building sector, especially drills, battery-operated screwdrivers or battery-operated tuckers.

  The method of using the electrochemical cell of the present invention in a device offers the advantage of longer operating time before charging. If the present invention achieves equal run times with electrochemical cells having lower energy density, heavier mass electrochemical cells must be accepted.

  The invention is further illustrated by the examples.

  Overview: Liters are understood to mean standard liters unless otherwise specified. Percentages relating to the present invention are by weight unless otherwise specified.

I. Examples of production Figures in% relate to weight percent, unless otherwise specified.

  The examples and comparative examples were carried out in a reactor system having a total volume of 8 l, the reactor system including a stirred tank having a volume of 7 l and a solid / liquid separator having a volume of 1 l. Using the separator, it was possible to remove the mother liquor from the stirred tank using a pump during the production of the particles of the present invention without simultaneously drawing solids.

  The reactor system was equipped with a pitch blade agitator and baffle. Stirrer power was measured from speed and torque using an electric motor with torque measurement. In addition, the reactor system had multiple metering units with metering pumps, as well as a pH measuring cathode and temperature sensor.

I. 1 Transition metal hydroxide TH. Production of 1 Initially, the reactor system was charged with 8 l of ammonium sulfate solution (36 g of (NH ₄ ) ₂ SO ₄ / l) and heated to 45 ° C.

  The contents of the agitation tank were continuously mixed and the contents were subjected to a mechanical treatment of about 45 watts. Thus, the specific power input in the stirred tank was about 6.4 watts per liter. In the separator, no stirrer power was introduced.

  In addition, there was a fill level sensor in the agitation tank, which controlled the discharge pump at the liquid side connection of the separation device so that the level in the agitation tank remained essentially constant. The solid was recycled back into the reactor from the separator.

  During the precipitation run, approximately 2 l of the gas space in the reactor system was purged with 40 l / h of nitrogen.

  The following aqueous solutions were used.

  Solution A: 0.825 mol nickel sulfate per kg solution, 0.33 mol cobalt sulfate per kg solution, and 0.495 mol manganese sulfate per kg solution, corresponding hydrate complex dissolved in water Manufactured by

Solution B: kg per 5.59 moles of NaOH solution, and the solution 1.55 mol per kg of _NH 3. Made from 25% NaOH and 25% ammonia solution.

  Solution C: 6.25 moles of NaOH per kg of solution.

  Solution D: Aluminum as 11.8 g sodium aluminate (technical grade sodium aluminate), dissolved in 1.15 kg water at about 50 ° C., pH 14.

  Solutions A and B were weighed into a stirring tank using a metering pump, and solution C was weighed so that the pH in the stirring tank was kept constant (pH control). Solution D was weighed in by a peristaltic pump. Ultrafine aluminum hydroxide particles formed from solution D during introduction under process conditions.

Experimental Procedure When the reaction temperature (45 ° C) was reached, the ammonium sulfate solution was adjusted to pH 11.82 as measured at 23 ° C by adding solution C. A metering pump was then used to meter solutions A and B at a constant mass flow rate (957/521 g / h) into the turbulent zone near the stirrer blades of the reactor system stirrer. Using a control device, the pH was kept constant at 11.8 (measured at 23 ° C.) by addition of solution C. This formed a suspension. After 20.5 hours, suspension D was further weighed (addition at about 0.18 l / h). After 6 hours, solution D was consumed. The mixture was then stirred for 15 minutes without feeding.

  This gave a suspension of transition metal hydroxide having a Ni: Co: Mn molar ratio of 5: 2: 3. The suspension was filtered through a suction filter and the filter cake was washed with water and dried under air at 105 ° C. for a period of 18 hours. The particles of the invention thus obtained have a composition of 31.0% by weight nickel, 12.5% by weight cobalt and 17.2% by weight manganese, respectively, in the form of hydroxides, It was in oxidized form. 3.6 kg of the particles of the invention were obtained. The aluminum content measured by atomic spectroscopy (ICP-OES) was 0.29%. The particles of the present invention were sieved (mesh size 32 μm; crude material: 0.1%) and the heavy bulk density was measured (1.97 kg / l). An aliquot was suspended in water and the particle size was measured by light scattering (Malvern Mastersizer 2000). The median particle size D50 was 10.6 μm and had a narrow particle size distribution (D10 = 7.8 μm; D90 = 14.5 μm).

  The outer shell thickness of the particles of the present invention was 0.5 μm to 0.6 μm, and the core diameter was about 9.6 μm to 9.8 μm. In the scanning electron micrograph, an aluminum oxide domain was evident, which had a diameter in the range of about 10 nm to 100 nm and was present only in the outer shell. The aluminum oxide domains were completely encapsulated by nickel-cobalt-manganese hydroxide.

II. 1 Method for the production of spherical particles of the invention TH. General method using one example:
TH. 1 was mixed intimately with ground lithium carbonate. The molar ratio of lithium to the total number of transition metals in 1 was 1.10. A portion (40 g) of this mixture was baked in a muffle furnace (air atmosphere; maximum temperature: 900 ° C .; heating rate 3 K / min; holding points 300 ° C. and 600 ° C .; holding time at each stage: 6 hours). Heat treatment was performed in a rectangular crucible made of sintered alumina. After cooling to room temperature, the fired material was triturated in a mortar and sieved (mesh size 32 μm; no crude material). About 30 g of the spherical particles SP. 1 was obtained as a powder with virtually no agglomerates. This could be processed to produce the electrode of the present invention.

II. 2 Alumina-containing comparative material C-SP. II. II. In a modification of the method according to 1, commercially available spherical metal hydroxide (Ni: Co: Mn = 5: 2: 3) and aluminum hydroxide powder (2 mol% Al with respect to the total of transition metals; D50 1 0.8 μm; 99.4% Al (OH) ₃ ). A roller mixer was used for mixing (80 rpm, 1 hour, 30 g bowl-diameter 10 mm diameter, batch size 30 g powder). The ground lithium carbonate is then converted into II. 1 in the same manner and the mixture is mixed for another 5 hours, the other procedure is II. 1 as described. About 30 g of comparative particles C-SP. 2 was obtained (aluminum content equal to SP.1).

II. 3 Alumina-containing comparative material C-SP. 3 In a similar manner, comparative particles C-SP. 3 was obtained.

III. General Methods for the Production of Electrodes of the Invention and Electrochemical Cells of the Invention Materials Used:
Binder (BM.1): Polymer of vinylidene fluoride as a solution, 10% by weight in NMP, Arkema, Inc. Available as KynarFlex® 2801.

Electrically conductive carbonaceous material:
Carbon 1: carbon black, BET surface area of about 60 m ² / g, commercially available as “Super C65” from Timcal.

  Carbon 2: Graphite, commercially available as “KS6” from Timcal.

General method using examples of particles (SP.1) of the invention:
When 0.661 g of carbon 1, 0.661 g of carbon 2 and 13.21 g of binder (BM.1) were mixed with the addition of 10.02 g of N-methylpyrrolidone (NMP), a paste was obtained. In the next step, 4.99 g of this paste was mixed with 4.00 g of the inventive particles (SP.1). An aluminum foil having a thickness of 30 μm was coated with the above-mentioned paste (active material input amount: about 9 mg / cm ² ). After drying at 105 ° C., a circular portion (diameter 19.8 mm) of the aluminum foil thus coated was punched out. Using the electrode obtained in this way, the electrochemical cell EC. 1 was produced. The electrolyte used was a 1 mol / l solution of LiPF ₆ in ethylene carbonate / dimethyl carbonate (1: 1 based on parts by weight). The anode consisted of a lithium foil separated from the cathode by a partition made of glass fiber paper.

  The cell was then assembled at room temperature and cycled at 25 ° C. The cycle current was 150 A / kg based on the cathode active material, and in the first few cycles rate characteristics were also measured at currents up to 975 A / kg. The selected voltage range was 3.0 volts to 4.3 volts.

  Charging was performed at 150 A / kg until the upper limit switch-off voltage was reached, then charging was accomplished at a constant voltage for an additional 30 minutes. Discharging was always performed until the lower limit switch-off voltage was reached.

  The capacity of cycles 40 and 80 are reported in Table 1. Starting from these data, the capacity drop for 100 cycles was calculated, corresponding to 2.5 times the cycle 40 to 80 drop.

  A comparison cell was made in a similar manner.

EC. 1: The cell comprises the material of the present invention.
C-EC. 2: The cell is a comparative material C-SP. 2 is provided.
C-EC. 3: The cell is a comparative material C-SP. 3 is provided.

Claims (15)

(A) at least one transition metal mixed hydroxide or transition metal mixed carbonate of at least three different transition metals selected from nickel, cobalt, manganese, iron, chromium and vanadium;
(B) Spherical particles containing at least one fluoride, oxide or hydroxide of Ba, Al, Zr or Ti,
The transition metal in the transition metal hydroxide (A) or transition metal carbonate (A) is mainly in the +2 oxidation state,
Fluoride (B) or oxide (B) or hydroxide (B) is present to the extent of at least 75% in the outer shell of spherical particles in the form of domains, and transition metal hydroxide (A) Or spherical particles encapsulated to the extent of at least 90% with transition metal carbonate (A).   The spherical particle according to claim 1, wherein one or more transition metals in the transition metal hydroxide (A) or transition metal carbonate (A) are present at least partially in the +3 or +4 oxidation state. The spherical particle according to claim 1, wherein the oxide (B) is selected from BaTiO ₃ , Al ₂ O ₃ and TiO ₂ .   Spherical particles according to any one of claims 1 to 3, having a median diameter (D50) in the range of 2 µm to 30 µm.   Spherical particles according to any one of the preceding claims, wherein the outer shell has an average thickness of 1% to 15% with respect to the diameter of the respective particles. The transition metal mixed hydroxide (A) has the general formula (I)
Ni _a Co _b Mn _c M _d O _e (OH) _f (I)
(Where the signs are defined as follows:
M is one or more transition metals selected from Mg and / or Fe, Cr and V;
a is in the range of 0.1 to 0.8;
b is in the range of 0.1 to 0.4;
c is in the range of 0.1 to 0.6;
d is in the range of zero to 0.2;
a + b + c + d = 1,
e is in the range of 0.05 to 0.5;
f is in the range of 0.5 to 1.9;
(The average oxidation state of Ni, Co and Mn is in the range of 2.1 to 3.2)
The spherical particle according to any one of claims 1 to 5 represented by: The transition metal mixed carbonate (A) has the general formula (II)
Ni _{a ′} Co _{b ′} Mn _{c ′} M _{d ′} O _{e ′} (OH) _j (CO ₃ ) _h (II)
(Where the signs are defined as follows:
M is one and / or a plurality of transition metals selected from Fe, Cr and V;
a ′ is in the range of 0.1 to 0.5;
b ′ is in the range of zero to 0.3;
c ′ is in the range of 0.1 to 0.75;
d ′ is in the range of zero to 0.2;
a ′ + b ′ + c ′ + d ′ = 1,
e ′ is in the range of zero to 0.6;
h is in the range of 0.4 to 1;
j is in the range of zero to 0.3)
The spherical particle according to any one of claims 1 to 5 represented by:   Spherical particles according to any one of the preceding claims, which have a heterogeneous composition and the mean standard deviation of the composition of nickel, cobalt and manganese is in each case at most 10 mol%.   The ratio of fluoride (B) or oxide (B) or hydroxide (B) is 0.3 mass% to 5 mass% with respect to transition metal hydroxide (A) or transition metal carbonate (A). The spherical particles according to at least one of claims 1 to 8, which are in the range of A method for producing spherical particles according to at least one of claims 1 to 9, comprising:
(A) First, a step of generating particles of transition metal hydroxide (A) or transition metal carbonate (A);
(B) Fluoride (B) or oxide (B) or hydroxide (B), or a solution comprising a salt of Ba, Al, Zr or Ti and optionally a water-soluble fluoride, particles according to step (a) And contacting at a different time or place from step (a);
(C) Further transition metal hydroxide (A) or transition metal carbonate (A) is produced during step (c) and thus obtained transition metal hydroxide (A) or transition metal carbonate Combining the salt (A) with the particles from step (a), wherein steps (b) and (c) can be carried out simultaneously or sequentially.   A method of using spherical particles according to at least one of claims 1 to 9 for the production of lithium-containing transition metal mixed oxides.   A method for producing a lithium-containing transition metal mixed oxide, the step of mixing the spherical particles according to at least one of claims 1 to 9 with at least one lithium compound; Reacting with each other at a temperature in the range of 1000 ° C.   A lithium-containing transition metal mixed oxide obtained by the method according to claim 12. A lithium-containing transition metal mixed oxide in particulate form,
(C) at least one mixed oxide of at least three different transition metals selected from nickel, cobalt, manganese, iron, chromium and vanadium and lithium;
(D) at least one fluoride or oxide of Ba, Al, Zr or Ti,
Fluoride (D) or oxide (D) is present to the extent of at least 75% in the outer shell of the particles in the form of domains and is encapsulated to the extent of at least 90% by oxide (C). Lithium-containing transition metal mixed oxide.   15. A method of using a lithium-containing transition metal mixed oxide according to claim 13 or 14 as a cathode material for a lithium ion battery or for its production.

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